Actinically-crosslinkable siloxane-containing copolymers

ABSTRACT

The invention provide a class of actinically-crosslinkable silicone-containing prepolymers obtained by functionalizing an intermediary copolymer to have two or more thiol or ethylenically-unsaturated groups covalently attached thereto, wherein the intermediary copolymer is an atom-transfer radical polymerization (ATRP) product of a reactive mixture comprising a polysiloxane ATRP macroinitiator and at least one hydrophilic vinylic monomer. The present invention is also related to silicone hydrogel contact lenses made from a prepolymer of the invention and methods for making the contact lenses in a cost-effective way and with high consistency and high fidelity to the original lens design.

This application claims the benefit under 35 U.S.C. §119 (e) of U.S.provisional application Ser. No. 61/180,453 filed on May 22, 2009,herein incorporated by reference in its entirety.

The present invention is related to a class of silicone-containingprepolymers and methods for making the same. In addition, the presentinvention is related to silicone hydrogel contact lenses made from thisclass of silicone-containing prepolymers.

BACKGROUND

In recent years, soft silicone hydrogel contact lenses become more andmore popular because of their high oxygen permeability and comfort. Mostcommercially available silicone hydrogel contact lenses are producedaccording to a conventional cast molding technique involving use ofdisposable plastic molds and a mixture of monomers in the presence orabsence of macromers. However, disposable plastic molds inherently haveunavoidable dimensional variations, because, during injection-molding ofplastic molds, fluctuations in the dimensions of molds can occur as aresult of fluctuations in the production process (temperatures,pressures, material properties), and also because the resultant moldsmay undergo non-uniformly shrinking after the injection molding. Thesedimensional changes in the mold may lead to fluctuations in theparameters of contact lenses to be produced (peak refractive index,diameter, basic curve, central thickness etc.) and to a low fidelity induplicating complex lens design.

Such disadvantages encountered in a conventional cast-molding techniquecan be overcome by using the so-called Lightstream Technology™ (CIBAVision), as illustrated in U.S. Pat. Nos. 5,508,317, 5,789,464,5,849,810, and 6,800,225, which are incorporated by reference in theirentireties. The Lightstream Technology™ involves (1) a lens-formingcomposition which is typically a solution of one or more substantiallypurified prepolymer with ethylenically unsaturated groups and whichgenerally is substantially free of monomers and crosslinking agents witha small molecular weight, (2) reusable molds produced in high precision,and (3) curing under a spatial limitation of actinic radiation (e.g.,UV). Lenses produced according to the Lightstream Technology™ can havehigh consistency and high fidelity to the original lens design, becauseof use of reusable, high precision molds. In addition, contact lenseswith high quality can be produced at relatively lower cost due to theshort curing time and a high production yield.

These prepolymers, however, possess ill-defined structures of individualsegments and usually have randomly distributed photo-crosslinkablefunctionalities, which causes poor reproducibility in synthesis and lensproperties.

In order to fully utilize the Lightstream Technology™ to make siliconehydrogel contact lenses, there is still a need for newactinically-crosslinkable prepolymers with well-defined structures,controlled composition and molecular weight. Such prepolymers could bewell suited for making silicone hydrogel contact lenses according to theLightstream Technology™.

SUMMARY OF THE INVENTION

In one aspect, the invention provides an actinically crosslinkableprepolymer. The prepolymer of the invention is obtained byfunctionalizing an intermediary copolymer to have two or moreactinically-crosslinkable groups covalently attached thereto, whereinthe intermediary copolymer is an atom-transfer radical polymerization(ATRP) product of a reactive mixture comprising a polysiloxane ATRPmacroinitiator and at least one hydrophilic vinylic monomer, wherein theactinically-crosslinkable groups are selected from the group consistingof ethylenically unsaturated groups, thiol groups, and combinationsthereof.

In another aspect, the invention provides a soft contact lens made froma lens-forming material including an actinically-crosslinkableprepolymer of the invention.

In a further aspect, the invention provides a method for producing softcontact lenses from an actinically-crosslinkable prepolymer of theinvention.

The invention also provides a polysiloxane ATRP macroinitiator.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well known and commonly employed inthe art.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A “silicone hydrogel contactlens” refers to a contact lens comprising a silicone hydrogel material.

A “hydrogel” or “hydrogel material” refers to a polymeric material whichcan absorb at least 10 percent by weight of water when it is fullyhydrated.

A “silicone hydrogel” refers to a silicone-containing hydrogel obtainedby copolymerization of a polymerizable composition comprising at leastone silicone-containing monomer or at least one silicone-containingmacromer or at least one crosslinkable silicone-containing prepolymer.

A “monomer” means a low molecular weight compound that can bepolymerized. Low molecular weight typically means average molecularweights less than 700 Daltons.

An “actinically-polymerizable monomer” refers to a monomer which can bepolymerized actinically. In accordance with the invention, anactinically-polymerizable monomer can be a vinylic monomer or a compoundcomprising two thiol groups. A compound with two thiol groups canparticipate in thiol-ene step-growth radical polymerization with amonomer with vinyl group to form a polymer. Step-growth radicalpolymerization can be used in making contact lenses, as described in acommonly-owned copending US patent application publication No.2008/0143958 A1, herein incorporated in reference in its entirety.

“Hydrophilic,” as used herein, describes a material or portion thereofthat will more readily associate with water than with lipids.

A “vinylic monomer”, as used herein, refers to a monomer that has onesole ethylenically unsaturated group and can be polymerized actinicallyor thermally.

The term “olefinically unsaturated group” or “ethylenticaly unsaturatedgroup” is employed herein in a broad sense and is intended to encompassany groups containing a >C═C< group. Exemplary ethylenically unsaturatedgroups include without limitation acryloyl

styrenyl, or other C═C containing groups.

As used herein, “actinically” in reference to curing, crosslinking orpolymerizing of a polymerizable composition, a prepolymer or a materialmeans that the curing (e.g., crosslinked and/or polymerized) isperformed by actinic irradiation, such as, for example, UV irradiation,ionized radiation (e.g. gamma ray or X-ray irradiation), microwaveirradiation, and the like. Thermal curing or actinic curing methods arewell-known to a person skilled in the art.

The term “ATRP” refers to atom-transfer radical polymerization, asunderstood by a person skilled in the art.

A “polysiloxane-containing ATRP macroinitiator” refers to a polymercontaining at least one polysiloxane segment and terminal organobromideor organochloride groups.

A “polysiloxane” segment refers to a divalent radical of

in which R₁ and R₂ are independently a monovalent C₁-C₁₀ alkyl, amonovalent C₁-C₁₀ aminoalkyl, a monovalent of C₁-C₁₀ hydroxyalkyl,C₁-C₁₀ ether, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ fluoroether or C₆-C₁₈ arylradical, -alk-(OCH₂CH₂)_(m)—OR₃, in which alk is C₁-C₆ alkylene divalentradical, R₃ is hydrogen or C₁-C₆ alkyl, and m is an integer of from 1 to10; n is an integer of 3 or higher.

The term “fluid” as used herein indicates that a material is capable offlowing like a liquid.

A “hydrophilic vinylic monomer” refers to a vinylic monomer which can bepolymerized to form a polymer that is water-soluble or can absorb atleast 10 percent by weight of water.

A “hydrophobic vinylic monomer”, as used herein, refers to a vinylicmonomer which is polymerized to form a polymer that is insoluble inwater and can absorb less than 10 percent by weight water.

A “macromer” refers to a medium and high molecular weight compound whichcan be polymerized and/or crosslinked. Medium and high molecular weighttypically means average molecular weights greater than 700 Daltons.

An “actinically-polymerizable macromer” refers to a macromer which canbe polymerized actinically. In accordance with the invention, anactinically-polymerizable macromer can be a macromer with one or moreethylenically unsaturated groups or with two or more thiol groups, whichcan participate in either free radical chain growth polymerization orthiol-ene step-growth radical polymerization. Preferably, a macromercontains ethylenically unsaturated groups and can be polymerizedactinically or thermally.

A “vinylic macromer” refers to a macromer which can be polymerizedactinically and comprises one or more ethylenically unsaturated groups.

A “prepolymer” refers to a starting polymer which contains two or moreactinocally crosslinkable groups and can be cured (e.g., crosslinked)actinically to obtain a crosslinked polymer having a molecular weightmuch higher than the starting polymer.

A “silicone-containing prepolymer” refers to a prepolymer which containssilicone and can be crosslinked actinically to obtain a crosslinkedpolymer having a molecular weight much higher than the starting polymer.

“Actinically crosslinkable groups” refers to ethylenically unsaturatedgroups or thiol groups.

“Molecular weight” of a polymeric material (including monomeric ormacromeric materials), as used herein, refers to the number-averagemolecular weight unless otherwise specifically noted or unless testingconditions indicate otherwise.

“Polymer” means a material formed by polymerizing one or more monomers,one or more macromers, and/or one or more prepolymers.

As used herein, the term “functionalize” in reference to a copolymer ora compound is intended to describe that one or more actinicallycrosslinkable groups have been covalently attached to a copolymer orcompound through the pendant or terminal functional groups of thecopolymer or the compound according to a coupling process.

As used herein, the term “multiple” refers to three or more.

A “photoinitiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of light. Suitablephotoinitiators include, without limitation, benzoin methyl ether,diethoxyacetophenone, a benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, Darocure® types, and Irgacure® types, preferablyDarocure® 1173, and Irgacure® 2959.

A “spatial limitation of actinic radiation” refers to an act or processin which energy radiation in the form of rays is directed by, forexample, a mask or screen or combinations thereof, to impinge, in aspatially restricted manner, onto an area having a well definedperipheral boundary. A spatial limitation of UV radiation is obtained byusing a mask or screen having a radiation (e.g., UV) permeable region, aradiation (e.g., UV) impermeable region surrounding theradiation-permeable region, and a projection contour which is theboundary between the radiation-impermeable and radiation-permeableregions, as schematically illustrated in the drawings of U.S. Pat. Nos.6,800,225 (FIGS. 1-11), and 6,627,124 (FIGS. 1-9), 7,384,590 (FIGS.1-6), and 7,387,759 (FIGS. 1-6), all of which are incorporated byreference in their entireties. The mask or screen allows to spatiallyprojects a beam of radiation (e.g., UV radiation) having across-sectional profile defined by the projection contour of the mask orscreen. The projected beam of radiation (e.g., UV radiation) limitsradiation (e.g., UV radiation) impinging on a lens-forming materiallocated in the path of the projected beam from the first molding surfaceto the second molding surface of a mold. The resultant contact lenscomprises an anterior surface defined by the first molding surface, anopposite posterior surface defined by the second molding surface, and alens edge defined by the sectional profile of the projected UV beam(i.e., a spatial limitation of radiation). The radiation used for thecrosslinking is a radiation energy, especially UV radiation, gammaradiation, electron radiation or thermal radiation, the radiation energypreferably being in the form of a substantially parallel beam in orderon the one hand to achieve good restriction and on the other handefficient use of the energy.

In the conventional cast-molding process, the first and second moldingsurface of a mold are pressed against each other to form acircumferential contact line which defines the edge of a result contactlens. Because the close contact of the molding surfaces can damage theoptical quality of the molding surfaces, the mold cannot be reused. Incontrast, in the Lightstream Technology™, the edge of a resultantcontact lens is not defined by the contact of the molding surfaces of amold, but instead by a spatial limitation of radiation. Without anycontact between the molding surfaces of a mold, the mold can be usedrepeatedly to produce high quality contact lenses with highreproducibility.

“Visibility tinting” in reference to a lens means dying (or coloring) ofa lens to enable the user to easily locate a lens in a clear solutionwithin a lens storage, disinfecting or cleaning container. It is wellknown in the art that a dye and/or a pigment can be used in visibilitytinting a lens.

“Dye” means a substance that is soluble in a lens-forming fluid materialand that is used to impart color. Dyes are typically translucent andabsorb but do not scatter light.

A “pigment” means a powdered substance (particles) that is suspended ina lens-forming fluid material in which it is insoluble.

“Surface modification” or “surface treatment”, as used herein, meansthat an article has been treated in a surface treatment process (or asurface modification process) prior to or posterior to the formation ofthe article, in which (1) a coating is applied to the surface of thearticle, (2) chemical species are adsorbed onto the surface of thearticle, (3) the chemical nature (e.g., electrostatic charge) ofchemical groups on the surface of the article are altered, or (4) thesurface properties of the article are otherwise modified. Exemplarysurface treatment processes include, but are not limited to, a surfacetreatment by energy (e.g., a plasma, a static electrical charge,irradiation, or other energy source), chemical treatments, the graftingof hydrophilic vinylic monomers or macromers onto the surface of anarticle, mold-transfer coating process disclosed in U.S. Pat. No.6,719,929 (herein incorporated by reference in its entirety), theincorporation of wetting agents into a lens formulation for makingcontact lenses proposed in U.S. Pat. Nos. 6,367,929 and 6,822,016(herein incorporated by references in their entireties), reinforcedmold-transfer coating disclosed in U.S. Patent Application No.60/811,949 (herein incorporated by reference in its entirety), and ahydrophilic coating composed of covalent attachment or physicaldeposition of one or more layers of one or more hydrophilic polymer ontothe surface of a contact lens.

“Post-curing surface treatment”, in reference to a silicone hydrogelmaterial or a soft contact lens, means a surface treatment process thatis performed after the formation (curing) of the hydrogel material orthe soft contact lens in a mold.

A “hydrophilic surface” in reference to a silicone hydrogel material ora contact lens means that the silicone hydrogel material or the contactlens has a surface hydrophilicity characterized by having an averagedwater contact angle of about 90 degrees or less, preferably about 80degrees or less, more preferably about 70 degrees or less, morepreferably about 60 degrees or less.

An “average contact angle” refers to a water contact angle (advancingangle measured by Wilhelmy Plate method), which is obtained by averagingmeasurements of at least 3 individual contact lenses.

An “antimicrobial agent”, as used herein, refers to a chemical that iscapable of decreasing or eliminating or inhibiting the growth ofmicroorganisms such as that term is known in the art. Preferred examplesof antimicrobial agent include without limitation silver salts, silvercomplexes, silver nanoparticles, silver-containing zeolites, and thelikes

“Silver nanoparticles” refer to particles which is made essentially ofsilver metal and have a size of less than 1 micrometer.

A “UV absorber” refers to a compound comprising a Ultra-violet absorbing(“UV-absorbing”) moiety capable of absorbing or screening out UVradiation in the region of 200 to 400 nm.

The intrinsic “oxygen permeability”, Dk, of a material is the rate atwhich oxygen will pass through a material. In accordance with theinvention, the term “oxygen permeability (Dk)” in reference to amaterial or a contact lens means an apparent oxygen permeability whichis measured with a sample (film or lens) having an average thicknessover the area being measured according to a coulometric method describedin Examples. Oxygen permeability is conventionally expressed in units ofbarrers, where “barrer” is defined as [(cm³ oxygen)(mm)/(cm²)(sec)(mmHg)]×10⁻¹⁰.

The “oxygen transmissibility”, Dk/t, of a lens or material is the rateat which oxygen will pass through a specific lens or material with anaverage thickness of t[in units of mm] over the area being measured.Oxygen transmissibility is conventionally expressed in units ofbarrers/mm, where “barrers/mm” is defined as [(cm³ oxygen)/(cm²)(sec)(mmHg)]×10⁻⁹.

The “ion permeability” through a lens correlates with the IonofluxDiffusion Coefficient. The Ionoflux Diffusion Coefficient, D (in unitsof [mm²/min]), is determined by applying Fick's law as follows:D=−n′/(A×dc/dx)where n′=rate of ion transport [mol/min]; A=area of lens exposed [mm²];dc=concentration difference [mol/L]; dx=thickness of lens [mm].

In general, the invention is directed to a class of actinicallycrosslinkable silicone-containing prepolymers comprising at least onepolysiloxane segment and hydrophilic chain segments each terminated withan actinically crosslinkable group. Such prepolymers can be used toprepare silicone hydrogel contact lenses, in particularly according tothe Lightstream Technology™ (CIBA Vision).

There are several potential unique features associated with use ofprepolymers of the invention in making silicone hydrogel contact lens.First, a prepolymer of the invention has well-defined structures,controlled composition, and molecular weight. The synthesis of suchprepolymer is reproducible. Lenses made from such prepolymer can haveconsistent properties. Second, a lens-forming formulation (polymerizablecomposition) can be a solution of the prepolymer which has beensubstantially purified (i.e., removing substantially starting materialsfor making the prepolymer). No lens extraction is necessary after curingof the lens. Third, a prepolymer of the invention can be curedactinically on a timescale of seconds. As such, prepolymers of theinvention can fully utilize the advantages provided by the LightstreamTechnology™ in make silicone hydrogel contact lenses at a relativelylower cost and at high consistency and high fidelity to the originallens design.

In one aspect, the invention provides an actinically crosslinkableprepolymer of formula (1) or (2)

in which

-   -   r₁ is an integer of 1 to 3, r₂ and r₂′ are either 0 or 1        provided that (r₂+r₂′) is an integer of 1, r₃ is an integer of 3        or 4;    -   G₁, G₂, G₃, and G₄ independent of each other are a linear or        branched C₁-C₁₀ alkylene divalent radical, a divalent radical of

in which q is an integer of from 1 to 5 and alk and alk′ independent ofeach other is a C₁-C₆ alkylene divalent radical (or so-called divalentaliphatic hydrocarbon radical or alkyl diradical), or a divalent radicalof —R′₁—X₅-E-X₆—R′₂— in which R′₂ and R′₂ independent of each other is alinear or branched C₁-C₁₀ alkylene divalent radical or a divalentradical of

as defined above, X₃ and X₄ independent of each other are a linkageselected from the group consisting of

in which R′ is H or C₁-C₈ alkyl, E is an alkyl diradical, a cycloalkyldiradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or anaryl diradical with up to 40 carbon atoms which may have ether, thio, oramine linkages in the main chain, provided that if r₂ is 0, then r₁ isinteger 2 or 3 and G₂ is a linear or branched C₁-C₁₀ alkyl radical or amonovalent radical of

in which q and alk′ are defined as above and alk″ is C₁-C₆ alkyl; X₁,X₂, X₃, and X₄ independent of each other are a linkage selected from thegroup consisting of a direct bond,

in which R′ is H or C₁-C₈ alkyl;PDMS is a polysiloxane divalent radical of formula (3)

-   -   in which ν is 0 or 1, ω is an integer of from 0 to 5, U₁ and U₂        independent of each other represent a divalent radical of        —R′₁—X₅-E-X₆—R′₂— as defined above or a divalent radical of

as defined above, D₁, D₂ and D₃ independently of each other are adivalent radical selected from the group consisting of—(CH₂CH₂O)_(t)—CH₂CH₂— in which t is an integer of 3 to 40,—CF₂—(OCF₂)_(a)—OCF₂— in which a and b independent of each other is aninteger of 0 to 10 provided that a+b is a number in the range of 10 to30, and a divalent group of formula (4)

-   -   in which R₃, R₄, R₅′, R₆, R₇, R₈, R₉ and R₁₀, independently of        one another, are C₁-C₈-alkyl, C₁-C₄ alkyl- or        C₁-C₄-alkoxy-substituted phenyl, fluoro(C₁-C₁₈-alkyl),        cyano(C₁-C₁₂-alkyl), -alk-(OCH₂CH₂)₁₁—OR₁₁ in which alk is        C₁-C₆-alkylene divalent radical, R₁₁ is C₁-C₆ alkyl and n is an        integer from 1 to 10, m and p independently of each other are an        integer of from 2 to 698 and (m+p) is from 5 to 700, provided        that at least one of D₁, D₂ and D₃ is represented by formula        (4);        L₁, L₂, and L₃ independent of each other are an organic radical        having a valence of (r₁+1), where the organic radical is a        linear or branched C₁-C₁₄ aliphatic radical, a C₅-C₄₅        cycloaliphatic or aliphatic-cycloaliphatic di-, tri-, or        tetra-valent radical, or a C₆-C₂₄ aromatic or araliphatic di-,        tri-, or tetra-valent radical, provided that each of L₁, L₂, and        L₃ has valence of (r₁+1); and        B₁ is a multivalent organic radical having a valence of r₃; and        A₁, A₂, and A₃ independently of one other are a monovalent        radical of formula (5)

in which r₄ is an integer of 0 or 1; X₇ is

in which R′ is H or C₁-C₈ alkyl; X₈ is a linkage selected from the groupconsisting of

in which R′ is H or C₁-C₈ alkyl; G₅ is a linear or branched C₁-C₁₀alkylene divalent radical, a divalent radical of

as defined above, or a divalent radical of —R′₁—X₅-E-X₆—R′₂— as definedabove; G₆ is a C₂-C₆ alkylene divalent radical; LC is a divalent radicalof a linear polymer chain of one or more hydrophilic vinylic monomers;and AX is an ethylenically unsaturated group or a thiol group.

Preferably, AX is radical of formula —X₈-G₇-X₉-Q, in which: X₈ is anlinkage as defined above; G₇ is a direct bond or a linear or branchedalkylene divalent radical; X₉ is a direct bond or a linkage selectedfrom the group consisting of

Q is an acryloyl group, a methacryloyl group, a vinyl group, an allylgroup, or a norbornenyl group.

Norbornenyl group refers to a monovalent radical of hydrocarbonincluding a cyclohexene ring bridged with a methylene group in the paraposition.

A prepolymer of formula (1) or (2) can be obtained in a two-stepprocess: (1) polymerizing, based on atom-transfer radical polymerization(ATRP), a reactive mixture comprising a polysiloxane ATRP macroinitiatorand at least one hydrophilic vinylic monomer to obtain an intermediarycopolymer comprising two or more hydrophilic polymer chains extendingfrom one or both of the two ends of a polysiloxane and each hydrophilicpolymer chain terminated with one bromine or chlorine atom; and (2)functionalizing the intermediary copolymer by substituting each terminalbromine or chlorine atom with a thiol or an ethylencially unsaturatedgroup.

In accordance with a preferred embodiment of the invention, the reactivemixture comprises a polysiloxane-containing ATRP macroinitiator offormula (6) or (7)

in which G₁, G₂, G₃, G₄, X₁, X₂, X₃, X₄, L₁, L₂, L₃, PDMS, r₁, r₂, r₂′,r₃, and B₁ are as defined above in formula (1) and (2); A₄, A₅, and A₆independently of one another are defined formula (8)

in which Y is Br or Cl; X₇, X₈, G₅, G₆, r4 are as defined above informula (5).

A polysiloxane ATRP macroinitiator of formula (6) can be prepared byreacting an oranic dibromide or dichloride, e.g., such as,2-chloropropionyl chloride or 2-chloroisobutyryl bromide, or preferably2-bromopropionyl bromide or 2-bromoisobutyryl bromide, with amono-(dihydroxyalkyl)-terminated polysiloxane, amono-(trihydroxyalkyl)-terminated polysiloxane, amono-(diaminoalkyl)-terminated polysiloxane, amono-(triaminoalkyl)-terminated polysiloxane, aα,ω-bis(hydroxyalkyl)-terminated polysiloxane, aα,ω-bis(dihydroxyalkyl)-terminated polysiloxane, aα,ω-bis(trihydroxyalkyl)-terminated polysiloxane, aα,ω-bis(aminoalkyl)-terminated polysiloxane, aα,ω-bis(diaminoalkyl)-terminated polysiloxane, or aα,ω-bis(triaminoalkyl)-terminated polysiloxane.

Polysiloxanes with one hydroxyl or amino group,α,ω-bis(hydroxyalkyl)-terminated polysiloxanes, andα,ω-bis(aminoalkyl)-terminated polysiloxanes are commercially availablefrom, e.g., from Aldrich, ABCR GmbH & Co., Fluorochem, or Gelest, Inc,Morrisville, Pa. Alternatively, they can be obtained by reacting2-mercaptoethanol or 2-aminoethanethiol with from vinyl-terminated oracryloyl-terminated polysiloxanes of various molecular weights based onthio-ene reaction or Michael Addition reaction mechanism known to aperson skilled in the art.

Polysiloxanes with one sole dihydroxyalkyl or trihydroxyalkyl terminalgroup can be obtained from a polysiloxane with one sole functional groupwell known to a person skilled in the art. For example, the amine groupof 3-amino-1,2-propanediol can react with carboxylic group of amonofunctionalized polysiloxane in the presence of a carbodiimide (i.e.,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC),N,N′-dicyclohexylcarbodiimide (DCC),1-cylcohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide) according to well-known carbodiimide-assisted couplingreaction, so as to form a polysiloxane with one sole dihydroxyalkylterminal group. Alternatively, thioglycerol can react withmono-3-methacryloxypropyl terminated, mono-butyl terminatedpolydimethylsiloxane based on Michael Addition reaction mechanism toform a polysiloxane with one sole dihydroxyalkyl terminal group.Further, 2-mercaptoethanol can react withmono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butylterminated polydimethylsiloxane based on Michael Addition reactionmechanism to form a polysiloxane with one sole dihydroxyalkyl terminalgroup. In addition, glycerol acrylate or glycerol methacrylate can reactwith a monothiol-terminated, monoalkyl-terminated polysiloxane based onMichael Addition reaction mechanism to form a polysiloxane with one soledihydroxyalkyl terminal group.

Similarly, polysiloxanes with one sole trihydroxyalkyl terminal groupcan be obtained by reacting N-[Tris(hydroxymethyl)methyl]acrylamide witha monothiol-terminated, monoalkyl-terminated polysiloxane, or byreacting thioglycerol withmono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butylterminated polydimethylsiloxane, based on Michael Addition reactionmechanism.

The above approaches can also be used to prepareα,ω-bis(dihydroxyalkyl)-terminated polysiloxanes andα,ω-bis(trihydroxyalkyl)-terminated polysiloxanes fromα,ω-difunctionalized polysiloxanes.

Similarly, the above approached can be used to prepare a polysiloxaneATRP macroinitiator of formula (7). In general, the preparation of apolysiloxane ATRP macroinitiator of formula (7) involves at least twosteps.

In the first step, a branching agent react with a di-functionalizedpolydisiloxane to form a branched polydisiloxane with three or four armseach having a terminal functional group for further reactions. Abranching agent is an organic compound comprising three or fourfunctional groups selected from the group consisting of amine groups,hydroxyl groups, carboxylic groups, isocyanate groups, thiol groups,acryloyl groups

methacryloyl groups

acid chloride groups, and epoxy groups. Preferably, a branching agentcomprises three functional groups and a polysiloxane ATRP macroinitiatorof formula (7) has three arms.

Examples of preferred branching agents include without limitationglycerol, diglycerol, 1,1,1-trishydroxymethylethane,1,1,1-trishydroxymethylpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol,erythritol, pentaerythritol, diethylenetriamine,N-2′-aminoethyl-1,3-propylenediamine, N,N-bis(3-aminopropyl)-amine,N,N-bis(6-aminohexyl)amine, triethylenetetramine, the isocyanuratetrimer of hexamethylene diisocyanate, 2,4,6-toluene triisocyanate, p,p′, p″-triphenylmethane triisocyanate, and the trifunctional trimer(isocyanurate) of isophorone diisocyanate, trimesoyl chloride,cyclohexane-1,3,5-tricarbonyl chloride, trimer acid chloride,triglycidylisocyanurate (TGIC), trimethylopropane trimethacrylate,pentaerythritol tetramethacrylate, triallyl isocyanurate, triallylcyanurate, aconitic acid, citric acid, 1,3,5-cyclohexanetricarboxylicacid, 1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid, 1,2,3 benzenetricarboxylic acid, and 1,2,4 benzene tricarboxylic acid.

It is well known in the art that a pair of matching functional groupscan form a covalent bond or linkage under known coupling reactionconditions, such as, oxidation-reduction conditions, dehydrationcondensation conditions, addition conditions, substitution (ordisplacement) conditions, Diels-Alder reaction conditions, cationiccrosslinking conditions, and epoxy hardening conditions. For example, anamino group reacts with aldehyde group to form a Schiff base which mayfurther be reduced; an amino group reacts with an acid chloride to forman amide linakge (—CO—N—); an amino group reacts with an isocyanate toform a urea linkage; an hydroxyl reacts with an isocyanate to form aurethane linkage; an hydroxyl reacts with an epoxy to form an etherlinkage (—O—); a hydroxyl reacts with an acid chloride to form an esterlinkage; an amino group reacts with carboxylic group in the presence ofa carbodiimide to form an amide linakge, a thiol group (—SH) reacts witha vinyl group based on thiol-ene reaction to for a thioether linakge(—S-—), a thio group reacts with an acryloyl or methacryloyl group basedon Michael Addition to form a thioether linkage.

A person skilled in the art will be able to select a branching agentwith three or four first functional groups and a polysiloxane with twoterminal second functional groups which can react with the firstfunctional groups to form covalent linkages based on a known couplingreaction discussed above or the like, thereby obtaining a branchedpolysiloxane with three or four arms.

In the second step, where the resultant branched polysiloxane with threeor four polysiloxane arms has terminal hydroxyl or amine groups, it canreact directly with, 2-chloropropionyl chloride, 2-chloroisobutyrylbromide, 2-bromopropionyl bromide, or 2-bromoisobutyryl bromide, to forma polysiloxane ATRP macroinitiator of formula (7). Alternatively, asdiscussed above, other terminal functional groups can be converted toterminal hydroxyl or amine groups or to terminal dihydroxyalkyl ortrihydroxyalkyl groups or to terminal diaminoalkyl or triaminoalkylgroups. Then those resultant polysiloxanes can be reacted with2-chloropropionyl chloride, 2-chloroisobutyryl bromide, 2-bromopropionylbromide or 2-bromoisobutyryl bromide, to form a polysiloxane ATRPmacroinitiator of formula (7).

It should be understood that the above described methods for preparing apolysiloxane ATRP macroinitiator of the invention is not exhaustive, butrather illustrative. A person skilled in the art will be able to selecta known coupling method to prepare a polysiloxane ATRP macroinitiator ofthe invention shown in formula (6) or (7).

It is also understood that a polysiloxane can have more than onepolydialkylsiloxane segment shown in formula (3), so-called a chainextended polysiloxane. Mono-functionalized and di-functionalizedchain-extended polysiloxanes can be prepared according to proceduressimilar to those described in U.S. Pat. Nos. 4,136,250, 4,486,577,4,605,712, 5,034,461, 5,416,132, and 5,760,100, herein incorporated byreference in their entireties.

A polysiloxane ATRP macroinitiator of the invention can be used toinitiate atom-transfer radical polymerization. It is believed that inATRP radicals are generated by the ATRP initiating moieties of apolysiloxane ATRP macroinitiator of the invention. Each ATRP initiatingmoiety undergoes a reversible redox process catalyzed by a transitionmetal compound such as cuprous halide (CuBr). Activation of the ATRPinitiating moiety involves the CuBr metal center undergoing an electrontransfer with simultaneous halogen atom abstraction and exapansion ofits coordinate sphere. The organic radical left behind after halogenatom abstraction is the reactive free radical that initiatespolymerization of one or more vinylic monomers present in a reactivemixture. After the ATRP, a polymeric chain composed of the one or morevinylic monomers is grown from each ATRP initiating moieties at theplace of its halogen atom and terminated with a halogen atom. Thisterminal halogen atom can be used as a reactive site to covalentlyattach an actinically-crosslinkable group, such as an ethylenciallyunsaturated group (e.g., ene group or acryloyl or methacryloyl group) ora thiol group.

Nearly any hydrophilic vinylic monomer can be used in the preparation ofthe intermediary copolymer for making a prepolymer of the invention.Suitable hydrophilic vinylic monomers are, without this being anexhaustive list, hydrophilic amide-type vinylic monomers,hydroxyl-substituted lower alkyl (C₁ to C₆) acrylates and methacrylates,hydroxyl-substituted lower alkyl vinyl ethers, N-vinylpyrrole,N-vinyl-2-pyrrolidone, 2-vinyloxazoline,2-vinyl-4,4′-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, olefinicallyunsaturated carboxylic acids having a total of 3 to 6 carbon atoms,amino(lower alkyl)-(where the term “amino” also includes quaternaryammonium), mono(lower alkylamino)(lower alkyl) and di(loweralkylamino)(lower alkyl)acrylates and methacrylates, allyl alcohol,N-vinyl alkylamide, N-vinyl-N-alkylamide,1-alkyl-3-methylene-2-pyrrolidone, 1-alkyl-5-methylene-2-pyrrolidone,and 5-alkyl-3-methylene-2-pyrrolidone, and the like.

Examples of preferred hydrophilic vinylic monomers areN,N-dimethylacrylamide (DMA), N,N-dimethylmethacrylamide (DMMA),2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethylacrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,1-n-propyl-3-methylene-2-pyrrolidone,1-n-propyl-5-methylene-2-pyrrolidone,1-isopropyl-3-methylene-2-pyrrolidone,1-isopropyl-5-methylene-2-pyrrolidone,1-n-butyl-3-methylene-2-pyrrolidone,1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate(HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate,hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxypropylmethacrylate hydrochloride, aminopropyl methacrylatehydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerolmethacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), allyl alcohol,vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500,methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinylisopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinylcaprolactam, and mixtures thereof. More preferably,N,N-dimethylacrylamide (DMA) or N,N-dimethylmethacrylamide (DMMA) and atleast one hydrophilic vinylic monomer other than DMA or DMMA are usedtogether used in the preparation of the intermediary copolymer formaking a prepolymer of the invention.

In one preferred embodiment, an actinically-crosslinakble prepolymer ofthe invention is represented by formula (1) in which r₂ is zero, In thispreferred embodiment, the prepolymer consists of one arm of polysiloxanechain having no actinically-crosslinkable terminal group and two orthree arms of hydrophilic polymer chains each terminated with anactinically-crosslinkable group.

In another preferred embodiment, an actinically-crosslinakble prepolymerof the invention is represented by formula (1) in which each of r₁ andr₂ is an integer of 1. In this preferred embodiment, the prepolymer hasa H-shape and consists of a polysiloxane chain or a chain-extendedpolysiloxane chain capped at each of its two ends with two hydrophilicpolymer chains.

In another preferred embodiment, an actinically-crosslinakble prepolymerof the invention is represented by formula (2) in which r₁ is an tigerof 1 and r₃ is an integer of 3. In this preferred embodiment, theprepolymer consists of three arms radiating from a branching agent, eacharm consisting of a polysiloxane or chain-extended polysiloxane chainwhich is connected at one of its ends to the branching agent and iscapped at the other end with a hydrophilic polymer chain.

In another preferred embodiment, the hydrophilic polymer chains (LC) ofan actinically-crosslinkable prepolymer of the invention is composed ofmonomeric units of DMA and/or one or more hydrophilic vinylic monomerother than DMA.

In another preferred embodiment, the hydrophilic polymer chains (LC) ofan actinically-crosslinkable prepolymer of the invention is composed ofmonomeric units of NVP and/or one or more hydrophilic vinylic monomerother than NVP.

In another preferred embodiment, the hydrophilic polymer chains (LC) ofan actinically-crosslinkable prepolymer of the invention is composed ofmonomeric units of 3-acryloylamino-1-propanol, N-hydroxyethylacrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide,2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA),hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerolmethacrylate (GMA), allyl alcohol, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500,or a combination thereof. In this preferred embodiment, the hydrophilicpolymer chains have a bottle-brush structure, i.e., shorthydroxyl-containing chains extending outwardly from one main hydrophilicpolymer chain.

In accordance with the invention, the reactive mixture for preparing anintermediary copolymer of the invention can further comprise one or moremembers selected from the group consisting of a silicone-containingvinylic monomer, a hydrophobic vinylic monomer free of silicone atom, apolymerizable UV-absorbing agent (i.e., a compound comprising a UVabsorbing moiety and an ethylenically unsaturated group), apolymerizable latent UV-absorbing agent (i.e., a compound comprising alatent UV absorbing moiety and an ethylenically unsaturated group). Itis understood that the weight percentage of those components should beless than about 10%, preferably less than about 5%, more preferably lessthan about 3% relative to the total weight of polymerization componentsother than polysiloxane ATRP macroinitiator.

Examples of preferred silicone-containing vinylic monomers includewithout limitation N-[tris(trimethylsiloxy)silylpropyl]methacrylamide,N-[tris(trimethylsiloxy)-silylpropyl]acrylamide,N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide,N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide,N-[tris(dimethylphenylsiloxy)silylpropyl]acrylamide,N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide,N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide,N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;3-methacryloxy propylpentamethyldisiloxane,tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS),(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane),(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane,3-methacryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane,N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propylvinyl carbonate,3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane,3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate,3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate,t-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinylcarbonate, and trimethylsilylmethyl vinyl carbonate). Most preferredsiloxane-containing (meth)acrylamide monomers of formula (1) areN-[tris(trimethylsiloxy)silylpropyl]acrylamide, TRIS,N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.

Examples of preferred hydrophobic vinylic monomers includemethylacrylate, ethyl-acrylate, propylacrylate, isopropylacrylate,cyclohexylacrylate, 2-ethylhexylacrylate, methylmethacrylate, ethylmethacrylate, propylmethacrylate, vinyl acetate, vinyl propionate, vinylbutyrate, vinyl valerate, styrene, chloroprene, vinyl chloride,vinylidene chloride, acrylonitrile, 1-butene, butadiene,methacrylonitrile, vinyl toluene, vinyl ethyl ether,perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornylmethacrylate, trifluoroethyl methacrylate, hexafluoro-isopropylmethacrylate, hexafluorobutyl methacrylate.

Any suitable polymerizable UV-absorbing agents can be used in theinvention. Preferably, a polymerizable UV-absorbing agent comprises abenzotriazole-moiety or a benzophenone-moiety. Examples of preferredpolymerizable UV absorbers include without limitation2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-methacryloxyethylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacryloxypropylphenyl)benzotriazole,2-hydroxy-4-acryloxy alkoxy benzophenone, 2-hydroxy-4-methacryloxyalkoxy benzophenone, allyl-2-hydroxybenzophenone,2-hydroxy-4-methacryloxy benzophenone.

A polymerizable latent UV-absorbing agent can be prepared from apolymerizable UV-absorbing agent described above according to any knownmethod known to a person skilled in the art. For example, abenzotriazole-moiety or a benzophenone-moiety can be reacted with aprotected labile group to convert a UV-absorbing moiety into a latentUV-absorbing moiety.

For a benzotriazole-type of UV-absorbing agent, the hydroxyl radical ofthe phenol moiety in a benzotriazole moiety can be replaced with aprotective labile group to render the agent essentially non-UV absorbing(i.e., the protective group essentially shifts the absorption propertiesof the compound so that the agent does not absorb as strongly in the 280to 400 nm range). Examples of protective labile groups include withoutlimitation acetyl radical, acetylalkylsilane, alkylether, andalkylester. These protective groups can be converted back to a hydroxylradical according to any known method after the lens is cured, thusrendering the lens UV-absorbing. For example, removal of protectivelabile groups can be performed by soaking the cured lens in saturatedbicarbonate solution and heating.

Similarly, at least one hydroxyl radical of the phenolic radical of abenzophenone moiety can be replaced with one of the aforementionedprotective labile groups to form a latent UV-absorbing moiety. Thelatent UV-absorbing moiety can be converted to a UV-absorbing moiety byremoving the protective labile group.

A polymerizable UV-absorbing agent or a polymerizable latentUV-absorbing agent is generally is present in the monomer mixture in anamount sufficient to render a contact lens, which is obtained from thecuring of the monomer mixture and is subjected to treatment to convertlatent UV-absorbing moieties if applicable, absorbing at least about 80percent of the UV light in the range of from about 280 nm to about 370nm that impinges on the lens. A person skilled in the art willunderstand that the specific amount of UV-absorbing agent used in themonomer mixture will depend on the molecular weight of the UV-absorbingagent and its extinction coefficient in the range from about 280 toabout 370 nm. In accordance with the invention, the monomer mixturecomprises about 0.2% to about 5.0%, preferably about 0.5% to about 2.5%,by weight of a UV-absorbing agent.

A reactive mixture for preparing an intermediary copolymer of theinvention preferably comprises a solvent which dissolves all of thedesirable components. Example of suitable solvents includes withoutlimitation, water, tetrahydrofuran, tripropylene glycol methyl ether,dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones(e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butylether, diethylene glycol methyl ether, ethylene glycol phenyl ether,propylene glycol methyl ether, propylene glycol methyl ether acetate,dipropylene glycol methyl ether acetate, propylene glycol n-propylether, dipropylene glycol n-propyl ether, tripropylene glycol n-butylether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether,tripropylene glycol n-butyl ether, propylene glycol phenyl etherdipropylene glycol dimethyl ether, polyethylene glycols, polypropyleneglycols, ethyl acetate, butyl acetate, amyl acetate, methyl lactate,ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol,1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol andexonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol,3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol,3-octanol, norborneol, tert-butanol, tert-amyl, alcohol,2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol,1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol,1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol,2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol,3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol,4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol,3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol,4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol,2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol,1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene,4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol,2-methoxy-2-methyl-2-propanol 2,3,4-trimethyl-3-pentanol,3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanoland 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amylalcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide,dimethyl formamide, dimethyl acetamide, dimethyl propionamide,N-methylpyrrolidinone, and mixtures thereof.

Where crosslinking of a prepolymer of the invention is based on themechanism of free radical chain-growth polymerization, the actinicallycrosslinkable groups of the prepolymer preferably comprises at least twoethylenically unsaturated groups. For example, the bromine or chlorineatoms of an intermediary copolymer prepared according to a proceduredescribed above can be substituted by an acryloyloxy or methacryloyloxygroup if it is reacted with acrylic or methacrylic acid, by anacryloylamino or methacryloylamino group if it is reacted withacrylamide or methacrylamide, by an allylcarboxy group if it is reactedwith allyl acid, or by an allylamino group if it is reacted withallylamine.

Where crosslinking of a prepolymer of the invention is based on themechanism of thiol-ene step-growth radical polymerization, theactinically crosslinkable groups of the prepolymer preferably comprisesat least two thiol groups or at least two ene-containing groups. An“ene-containing group” is intended to describe a mono-valent or divalentradical that contains a carbon-carbon double which is not directlylinked to a carbonyl group (—CO—), nitrogen atom, or oxygen atom.Examples of preferred ene-groups are vinyl, allyl and norbornenylgroups. Ene-groups can be introduced into an intermediary copolymeraccording to any known methods. For example, the bromine or chlorineatoms of an intermediary copolymer prepared according to a proceduredescribed above can be substituted by 5-Norbornene-2-carboxy group if itis reacted with 5-Norbornene-2-carboxylic acid.

Thiol groups can be introduced into an intermediary copolymer accordingto S_(N)2 displacement with a sulfur nuleophile such as thoiurea,(NH₂)₂C═S, as known to a person skilled in the art.

Preferably, a resultant prepolymer of the invention is substantiallypurified in a manner known to a person skilled in the art, for example,by precipitation with organic solvents, such as acetone, filtration andwashing, extraction in a suitable solvent, dialysis or ultrafiltration,ultrafiltration being especially preferred. The prepolymers ispreferably purified to be in an extremely pure form, for example in theform of concentrated solutions that are free, or at least substantiallyfree, from reaction products, such as salts, and from startingmaterials, such as, for example, non-polymeric constituents. Thepreferred purification process for the prepolymers used in the processaccording to the invention, ultrafiltration, can be carried out in amanner known to a person skilled in the art. It is possible for theultrafiltration to be carried out repeatedly, for example from two toten times. Alternatively, the ultrafiltration can be carried outcontinuously until the selected degree of purity is attained. Theselected degree of purity can in principle be as high as desired. Byusing such prepolymers in making contact lenses, the obtained lenseswill not require subsequent purification such as, for example, costlyand complicated extraction of unpolymerized matrix-forming material.

A prepolymer of the invention can be used in preparing silicone hydrogelcontact lenses or other medical devices.

In another aspect, the invention provides a soft contact lens. The softcontact lens of the invention comprises: a silicone hydrogel materialthat is obtained by curing a lens-forming material in a mold, whereinthe lens-forming material comprises an actinically crosslinkableprepolymer of formula (1) or (2) as described above.

In accordance with the invention, a lens-forming material is a fluidcomposition, which can be a solution or a melt at a temperature fromabout 20° C. to about 85° C. Preferably, a lens-forming material is asolution of at least one prepolymer of the invention and other desirablecomponents in water, or an organic solvent, or a mixture of water andone or more organic solvents.

A solution of at least one prepolymer of the invention can be preparedby dissolving the prepolymer and other components in any suitablesolvent known to a person skilled in the art. Examples of suitablesolvents are described above.

All of the various embodiments of the prepolymer of the inventiondescribed above can be used in this aspect of the invention.

The lens-forming material can but preferably does not comprise one ormore members selected from the group consisting of a hydrophilic vinylicmonomer, a silicone-containing vinylic monomer, a hydrophobic vinylicmonomer free of silicone atom, a crosslinking agent (i.e., compoundswith two or more ethylenically unsaturated groups and with molecularweight less than 700 Daltons). However, the amount of those componentsshould be low such that the final ophthalmic device does not containunacceptable levels of unpolymerized vinylic monomers and/orcrosslinking agents. The presence of unacceptable levels ofunpolymerized monomers and/or crosslinking agents will requireextraction to remove them, which requires additional steps that arecostly and inefficient. But preferably, the lens-forming material issubstantially free of vinylic monomer and crosslinking agent (i.e.,preferably about 2% or less, more preferably about 1% or less, even morepreferably about 0.5% or less by weight of combination of vinylicmonomer and crosslinking agent).

All of various embodiments of hydrophilic vinylic monomers,silicone-containing vinylic monomers, and hydrophobic vinylic monomersfree of silicone atoms can be used in this aspect of the invention.

Examples of preferred crosslinking agents include without limitationtetra(ethyleneglycol) diacrylate, tri(ethyleneglycol) diacrylate,ethyleneglycol diacylate, di(ethyleneglycol) diacrylate,tetraethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate,ethyleneglycol dimethacylate, di(ethyleneglycol) dimethacrylate,trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate,bisphenol A dimethacrylate, vinyl methacrylate, ethylenediaminedimethyacrylamide, glycerol dimethacrylate, triallyl isocyanurate,triallyl cyanurate, allylmethacrylate, dimers (e.g.,1,3-bis(methacrylamidopropyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane,1,3-bis(N-methacrylamidopropyl)-1,1,3,3-tetrakis-(trimethylsiloxy)disiloxane,1,3-bis(methacrylamidobutyl)-1,1,3,3-tetrakis(trimethylsiloxy)-disiloxane,1,3-bis(acrylamidopropyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane,1,3-bis(methacryloxyethylureidopropyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane)disclosed in U.S. Pat. No. 4,711,943 (herein incorporated by referencein its entirety), and combinations thereof. A preferred cross-linkingagent is tetra(ethyleneglycol) diacrylate, tri(ethyleneglycol)diacrylate, ethyleneglycol diacylate, di(ethyleneglycol) diacrylate,triallyl isocyanurate, or triallyl cyanurate.

It must be understood that a lens-forming material can also comprisevarious components, such as, for example, polymerization initiators(e.g., photoinitiator or thermal initiator), a visibility tinting agent(e.g., dyes, pigments, or mixtures thereof), a polymerizableUV-absorbing agent, a polymerizable latent UV-absorbing agent,antimicrobial agents (e.g., preferably silver nanoparticles), bioactiveagent, leachable lubricants, and the like, as known to a person skilledin the art.

All various embodiments of polymerizable UV-absorbing agents andpolymerizable latent UV-absorbing agents can be used in this aspect ofthe invention.

Initiators, for example, selected from materials well known for such usein the polymerization art, may be included in the lens-forming materialin order to promote, and/or increase the rate of, the polymerizationreaction. An initiator is a chemical agent capable of initiatingpolymerization reactions. The initiator can be a photoinitiator or athermal initiator.

A photoinitiator can initiate free radical polymerization and/orcrosslinking by the use of light. Suitable photoinitiators are benzoinmethyl ether, diethoxyacetophenone, a benzoylphosphine oxide,1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types,preferably Darocur 1173® and Darocur 2959®. Examples of benzoylphosphineinitiators include 2,4,6-trimethylbenzoyldiphenylophosphine oxide;bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators which can be incorporated, for example, into a macromeror can be used as a special monomer are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329, hereinincorporated by reference in its entirety. The polymerization can thenbe triggered off by actinic radiation, for example light, in particularUV light of a suitable wavelength. The spectral requirements can becontrolled accordingly, if appropriate, by addition of suitablephotosensitizers

Examples of preferred pigments include any colorant permitted in medicaldevices and approved by the FDA, such as D&C Blue No. 6, D&C Green No.6, D&C Violet No. 2, carbazole violet, certain copper complexes, certainchromium oxides, various iron oxides, phthalocyanine green,phthalocyanine blue, titanium dioxides, etc. See Marmiom DM Handbook ofU.S. Colorants for a list of colorants that may be used with the presentinvention. A more preferred embodiment of a pigment include (C.I. is thecolor index no.), without limitation, for a blue color, phthalocyanineblue (pigment blue 15:3, C.I. 74160), cobalt blue (pigment blue 36, C.I.77343), Toner cyan BG (Clariant), Permajet blue B2G (Clariant); for agreen color, phthalocyanine green (Pigment green 7, C.I. 74260) andchromium sesquioxide; for yellow, red, brown and black colors, variousiron oxides; PR122, PY154, for violet, carbazole violet; for black,Monolith black C—K (CIBA Specialty Chemicals).

The bioactive agent incorporated in the polymeric matrix is any compoundthat can prevent a malady in the eye or reduce the symptoms of an eyemalady. The bioactive agent can be a drug, an amino acid (e.g., taurine,glycine, etc.), a polypeptide, a protein, a nucleic acid, or anycombination thereof. Examples of drugs useful herein include, but arenot limited to, rebamipide, ketotifen, olaptidine, cromoglycolate,cyclosporine, nedocromil, levocabastine, lodoxamide, ketotifen, or thepharmaceutically acceptable salt or ester thereof. Other examples ofbioactive agents include 2-pyrrolidone-5-carboxylic acid (PCA), alphahydroxyl acids (e.g., glycolic, lactic, malic, tartaric, mandelic andcitric acids and salts thereof, etc.), linoleic and gamma linoleicacids, and vitamins (e.g., B5, A, B6, etc.).

Examples of leachable lubricants include without limitation mucin-likematerials (e.g., polyglycolic acid) and non-crosslinkable hydrophilicpolymers (i.e., without ethylenically unsaturated groups).

Any hydrophilic polymers or copolymers without any ethylenicallyunsaturated groups can be used as leachable lubricants. Preferredexamples of non-crosslinkable hydrophilic polymers include, but are notlimited to, polyvinyl alcohols (PVAs), polyamides, polyimides,polylactone, a homopolymer of a vinyl lactam, a copolymer of at leastone vinyl lactam in the presence or in the absence of one or morehydrophilic vinylic comonomers, a homopolymer of acrylamide ormethacrylamide, a copolymer of acrylamide or methacrylamide with one ormore hydrophilic vinylic monomers, polyethylene oxide (i.e.,polyethylene glycol (PEG)), a polyoxyethylene derivative,poly-N—N-dimethylacrylamide, polyacrylic acid, poly 2 ethyl oxazoline,heparin polysaccharides, polysaccharides, and mixtures thereof. Thenumber-average molecular weight M_(n) of the non-crosslinkablehydrophilic polymer is preferably from 5,000 to 500,000, more preferablyfrom 10,000 to 300,000, even more preferably from 20,000 to 100,000.

Lens molds for making contact lenses are well known to a person skilledin the art and, for example, are employed in cast molding or spincasting. For example, a mold (for cast molding) generally comprises atleast two mold sections (or portions) or mold halves, i.e. first andsecond mold halves. The first mold half defines a first molding (oroptical) surface and the second mold half defines a second molding (oroptical) surface. The first and second mold halves are configured toreceive each other such that a lens forming cavity is formed between thefirst molding surface and the second molding surface. The moldingsurface of a mold half is the cavity-forming surface of the mold and indirect contact with lens-forming material.

Methods of manufacturing mold sections for cast-molding a contact lensare generally well known to those of ordinary skill in the art. Theprocess of the present invention is not limited to any particular methodof forming a mold. In fact, any method of forming a mold can be used inthe present invention. The first and second mold halves can be formedthrough various techniques, such as injection molding or lathing.Examples of suitable processes for forming the mold halves are disclosedin U.S. Pat. Nos. 4,444,711 to Schad; 4,460,534 to Boehm et al.;5,843,346 to Morrill; and 5,894,002 to Boneberger et al., which are alsoincorporated herein by reference.

Virtually all materials known in the art for making molds can be used tomake molds for preparing ocular lenses. For example, polymericmaterials, such as polyethylene, polypropylene, polystyrene, PMMA, acyclic olefin copolymer (such as for example, Topas®COC grade 8007-S10(clear amorphous copolymer of ethylene and norbornene) from Ticona GmbHof Frankfurt, Germany and Summit, N.J., Zeonex® and Zeonor® from ZeonChemicals LP, Louisville, Ky.), polymethylmethacrylate (PMMA),polyoxymethylene from DuPont (Delrin), Ultem® (polyetherimide) from G.E.Plastics, PrimoSpire®, or the like can be used. Other materials thatallow UV light transmission could be used, such as, quartz, glass,sapphire, CaF₂.

In a preferred embodiment, reusable molds can be used. Examples ofreusable molds suitable for spatial limitation of radiation includewithout limitation those disclosed in U.S. Pat. Nos. 6,800,225,6,627,124, 7,384,590, and 7,387,759, which are incorporated by referencein their entireties. In this aspect, the lens-forming material is pouredinto a mold consisting of two mold halves not touching each other buthaving a thin gap of annular design arranged between them. The gap isconnected to the mold cavity, so that excess lens-forming material canflow into the gap. Instead of polypropylene molds that can be used onlyonce, it is possible for reusable quartz, glass, sapphire or CaF₂ moldsto be used, since, following the production of a lens, these molds canbe cleaned rapidly and effectively to remove unreacted materials andother residues, using water or a suitable solvent, and can be dried withair. Reusable molds can also be made of a cyclic olefin copolymer (suchas for example, Topas® COC grade 8007-S10 (clear amorphous copolymer ofethylene and norbornene) from Ticona GmbH of Frankfurt, Germany andSummit, N.J., Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville,Ky.), polymethylmethacrylate (PMMA), polyoxymethylene from DuPont(Delrin), Ultem® (polyetherimide) from G.E. Plastics, PrimoSpire®.Because of the reusability of the mold halves, a relatively high outlaycan be expended at the time of their production in order to obtain moldsof extremely high precision and reproducibility. Since the mold halvesdo not touch each other in the region of the lens to be produced, i.e.the cavity or actual mold faces, damage as a result of contact is ruledout. This ensures a high service life of the molds, which, inparticular, also ensures high reproducibility of the contact lenses tobe produced and high fidelity to the lens design.

In accordance with the invention, the lens-forming material can beintroduced (dispensed) into a cavity formed by a mold according to anyknown methods.

After the lens-forming material is dispensed into the mold, it ispolymerized to produce a contact lens. Crosslinking may be initiated inthe mold e.g. by means of actinic radiation, such as UV irradiation,ionizing radiation (e.g., gamma or X-ray irradiation). Where prepolymersof the invention are the polymerizable components in the lens-formingmaterial, the mold containing the lens-forming material can be exposedto a spatial limitation of actinic radiation to crosslink theprepolymers.

The crosslinking according to the invention may be effected in a veryshort time, e.g. in ≦3 minutes, preferably in ≦2 minutes, morepreferably in ≦1 minute, most preferably in 5 to 50 seconds.

Opening of the mold so that the molded article can be removed from themold may take place in a manner known per se.

The molded contact lenses can further subject to further processes, suchas, for example, lens extraction with an organic solvent (e.g., thosedescribed above for preparing a lens forming material), hydration (in awater or an aqueous solution of a wetting agent), surface treatment,packaging in lens packages with a packaging solution which can contain awetting agent (e.g., a hydrophilic polymer described above) and/or aviscosity-enhancing agent (e.g., methyl cellulose (MC), ethyl cellulose,hydroxymethylcellulose, hydroxyethyl cellulose (HEC),hydroxypropylcellulose (HPC), hydroxypropylmethyl cellulose (HPMC), or amixture thereof); sterilization (e.g., autoclave); and the like.

A contact lens of the invention has an oxygen permeability of preferablyat least about 40 barrers, more preferably at least about 60 barrers,even more preferably at least about 80 barrers. In accordance with theinvention, an oxygen permeability is an apparent (directly measured whentesting a sample with a thickness of about 100 microns) oxygenpermeability according to procedures described in Examples.

A contact lens of the invention has an elastic modulus of about 2.0 MPaor less, preferably about 1.5 MPa or less, more preferably about 1.2 orless, even more preferably from about 0.4 MPa to about 1.0 MPa.

A contact lens of the invention further has an Ionoflux DiffusionCoefficient, D, of, preferably at least about 1.5×10⁻⁶ mm²/min, morepreferably at least about 2.6×10⁻⁶ mm²/min, even more preferably atleast about 6.4×10⁻⁶ mm²/min.

A contact lens of the invention further has a water content ofpreferably from about 15% to about 65%, more preferably from about 20%to about 50% by weight when fully hydrated. The water content of asilicone hydrogel contact lens can be measured according to BulkTechnique as disclosed in U.S. Pat. No. 5,849,811.

In a further aspect, the invention provides a method for producing softcontact lenses. The method comprises the steps of: providing a mold formaking a soft contact lens, wherein the mold has a first mold half witha first molding surface defining the anterior surface of a contact lensand a second mold half with a second molding surface defining theposterior surface of the contact lens, wherein said first and secondmold halves are configured to receive each other such that a cavity isformed between said first and second molding surfaces; introduce alens-forming material into the cavity, wherein the lens-forming materialcomprises an actinically crosslinkable prepolymer of formula (1) or (2)as described above; and actinically irradiating the lens formingmaterial in the cavity to form a contact lens.

All of the various embodiments of the molds, actinically-crosslinkableprepolymers, lens-forming materials, and spatial limitation ofradiation, and contact lens of the invention described above can be usedin this aspect of the invention.

All of the various embodiments of the reactive mixture described abovecan be used in this aspect of the invention.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. In order to better enable the reader tounderstand specific embodiments and the advantages thereof, reference tothe following non-limiting examples is suggested. However, the followingexamples should not be read to limit the scope of the invention.

Example 1 Oxygen Permeability Measurements

The oxygen permeability of a lens and oxygen transmissibility of a lensmaterial is determined according to a technique similar to the onedescribed in U.S. Pat. No. 5,760,100 and in an article by Winterton etal., (The Cornea: Transactions of the World Congress on the Cornea 111,H.D. Cavanagh Ed., Raven Press: New York 1988, pp 273-280), both ofwhich are herein incorporated by reference in their entireties. Oxygenfluxes (J) are measured at 34° C. in a wet cell (i.e., gas streams aremaintained at about 100% relative humidity) using a Dk1000 instrument(available from Applied Design and Development Co., Norcross, Ga.), orsimilar analytical instrument. An air stream, having a known percentageof oxygen (e.g., 21%), is passed across one side of the lens at a rateof about 10 to 20 cm³/min., while a nitrogen stream is passed on theopposite side of the lens at a rate of about 10 to 20 cm³/min. A sampleis equilibrated in a test media (i.e., saline or distilled water) at theprescribed test temperature for at least 30 minutes prior to measurementbut not more than 45 minutes. Any test media used as the overlayer isequilibrated at the prescribed test temperature for at least 30 minutesprior to measurement but not more than 45 minutes. The stir motor'sspeed is set to 1200±50 rpm, corresponding to an indicated setting of400±15 on the stepper motor controller. The barometric pressuresurrounding the system, P_(measured), is measured. The thickness (t) ofthe lens in the area being exposed for testing is determined bymeasuring about 10 locations with a Mitotoya micrometer VL-50, orsimilar instrument, and averaging the measurements. The oxygenconcentration in the nitrogen stream (i.e., oxygen which diffusesthrough the lens) is measured using the DK1000 instrument. The apparentoxygen permeability of the lens material, Dk_(app), is determined fromthe following formula:Dk _(app) =Jt/(P _(oxygen))where

J=oxygen flux [microliters O₂/cm²-minute]

P_(oxygen)=(P_(measured)−P_(water) vapor)=(% O₂ in air stream) [mmHg]=partial pressure of oxygen in the air stream

P_(measured)=barometric pressure (mm Hg)

P_(water) vapor=0 mm Hg at 34° C. (in a dry cell) (mm Hg)

P_(water) vapor=40 mm Hg at 34° C. (in a wet cell) (mm Hg)

t=average thickness of the lens over the exposed test area (mm)

where Dk_(app) is expressed in units of barrers.

The oxygen transmissibility (Dk/t) of the material may be calculated bydividing the oxygen permeability (Dk_(app)) by the average thickness (t)of the lens.

Ion Permeability Measurements.

The ion permeability of a lens is measured according to proceduresdescribed in U.S. Pat. No. 5,760,100 (herein incorporated by referencein its entirety. The values of ion permeability reported in thefollowing examples are relative ionoflux diffusion coefficients(D/D_(ref)) in reference to a lens material, Alsacon, as referencematerial. Alsacon has an ionoflux diffusion coefficient of 0.314×10⁻³mm²/minute.

Water Contact Angle (WCA) Measurements.

Water contact angle (WCA) measurements are performed by the sessile dropmethod with a DSA 10 drop shape analysis system from Krüss GmbH, Germanywith pure water (Fluka, surface tension 72.5 mN/m at 20° C.). Formeasurement purposes a contact lens is taken off the storage solutionwith tweezers and excess storage solution is removed by gentle shaking.The contact lens are placed on the male part of a lens mold and gentlyblotted with a dry and clean cloth. A water droplet (approximately 1 μl)is then dosed on the lens apex, and the change of the contact angle overtime of this water droplet (WCA(t), circle fitting mode) is monitored.The WCA is calculated by the extrapolation of the graph WCA(t) to t=0.

Example 2 A. Difunctional PDMS Macroinitiator

This example illustrates how to prepare prepolymers of the invention.

Preparation According to Scheme 1.

200 g (37 mmol) of α,ω-bis(hydroxyethoxypropyl)-terminated PDMS(KF-6003, MW≈5400 g/mol), 15.6 mL of diisopropylethylamine (90 mmol),and 1.2 L of hexanes are added in a 2 L round bottom flask. After thereaction mixture is cooled to 0° C. using an ice bath, 19.4 g (90 mmol)of 2-bromo-propionyl bromide in 60 mL of hexanes is added dropwise intothe flask through an addition funnel. The reaction mixture is allowed towarm to room temperature and reacted for 12 hours with stirring. Afterfiltration, the organic solution is washed with a saturated sodiumbiocarbonate solution (400 mL×2), followed by de-ionized water (400mL×2). The organic phase is collected and dried over using anhydrousmagnesium sulfate. After passing through a silica column and removingthe solvent under vacuum, a slightly yellowish oil like product iscollected (170 g, 85%). The product is confirmed using ¹H NMR. Thefunctionality is determined to be >95% (based on the ¹H-NMR data).

B. Tertrafunctional PDMS Macroinitiator

Preparation According to Scheme 2.

200 g (49 mmol) of α,ω-bis(3-methacryloxypropyl)-terminated PDMS(FM7721, MW≈4100 g/mol) is dissolved in 1 L of atetrahydrofuran/2-propanol mixture (1/1 V/V) in a 2 L round bottomflask, followed by adding 45 mL of KOH solution (0.1 N in methanol) and17.3 g (160 mmol) of 1-thioglycerol. The reaction is carried out at roomtemperature and monitored by titrating with an iodine solution in water(0.1 N). After reaction for 17 h at room temperature, 45 mL of HClsolution (0.1 N in methanol) is added to neutralize the reactionsolution. After removing all the solvent, the residuals are dissolved in1 L of methylene chloride and extracted with de-ionized water (500mL×4). The organic phase is collected and dried over anhydrous magnesiumsulfate. After passing through a silica column and removing the solvent,a slightly yellowish oil like product is obtained (178 g, 89%). Thefunctionality is determined to be greater than 95% (based on the ¹H-NMRdata).

178 g (37 mmol) of aforementioned tetra-OH terminated PDMS and 31.8 mL(222 mmol) of triethylamine are dissolved in 1 L of methylene chloridein a 2 L round bottom flask. After the reaction mixture is cooled to 0°C. using an ice bath, 23.3 ml (222 mmol) of 2-bromo-propionyl bromide in60 mL of hexanes is added dropwise through an addition funnel. Thereaction mixture is allowed to warm to room temperature and react for 16hours. After filtration, the organic solution is washed with sodiumhydroxide solution (0.037 mol/L in water, 800 ml×2) till the water layerbecomes basic. The organic phase is then washed with HCl solution (pH=4,800 mL×3) till the water layer becomes neutral, followed by deionizedwater (400 mL×2). The organic phase is collected and dried overanhydrous magnesium sulfate. After passing through a silica column andremoving the solvent, a pale yellowish oil like product is collected(156 g, 88%). The product is confirmed by ¹H NMR. The functionality isdetermined to be greater than 95% (based on the ¹H-NMR data).

Example 3

Actinically-crosslinkable prepolymers are prepared according to scheme 3as follows.

A. Synthesis of Br-PHEA-PDMS-PHEA-Br Block Copolymer

20 g (3.7 mmol) of difunctional PDMS macroinitiator (5400 g/mol)(prepared in Example 2, A), 42 mL (362 mmol) of 2-hydroxyethylacrylate(HEA), 0.04 g (0.19 mmol) of CuBr₂, 0.52 mL (2 mmol) oftris(2-aminoethyl amine) (Me₆TREN), and 160 ml of t-amyl alcohol areadded to a 500 mL Schlenk flask. After four cycles of freeze-pump-thaw(20 minutes per cycle), 0.26 g (1.81 mmol) of CuBr is added to the flaskunder positive N₂ flow. The reaction is carried out at 40° C. in the oilbath. The monomer conversion is monitored by gas chromatography. At atargeted monomer conversion, the reaction is stopped by opening theflask to air. The reaction mixture is diluted with THF and passedthrough a neutral aluminum oxide column. After addition of 5 mg of4-methoxyphenol, the solvent is removed by rotavap. The concentratedsolution is then precipitated into acetonitrile (800 mL). Afterfiltration, polymer (38 g) is obtained. The resultant polymer ofBr-PHEA-PDMS-PHEA-Br has a molecular weight of 12,360 g/mol and 44 w %PDMS.

B. Synthesis of PHEA-PDMS-PHEA Macromer Containing Acrylate Groups

10 g (0.81 mmol) of Br-PHEA-PDMS-PHEA-Br is dissolved in 50 mL of THF ina 100 mL round bottom flask, followed by addition of 0.42 mL (6 mmol) ofacrylic acid. 0.9 mL (6 mmol) of 1,8-Diazabicyclo[5,4,0]-udec-7-ene(DBU) is then slowly added to the reaction solution within 5 minutes.After reaction for 24 hours at room temperature, the polymer is purifiedvia ultrafiltration (3K MWCO) and dried via freeze-dry. 7.5 g of finalproduct is obtained. The MW of the prepolymer: 12360 g/mol (¹H NMR); Thedouble bond content: 0.113 meq/g (based on ¹H NMR).

C. Synthesis of PHEA-PDMS-PHEA Macromer Containing Norbornene Groups

10 g (0.81 mmol) of Br-PHEA-PDMS-PHEA-Br is dissolved in 50 mL of THF ina 100 mL round bottom flask, followed by addition of 0.68 mL (5.6 mmol)of 5-Norbornene-2-carboxylic acid. 0.83 mL (5.6 mmol) of1,8-Diazabicyclo[5,4,0]-udec-7-ene (DBU) is then slowly added to thereaction solution within 5 minutes. After reaction for 24 hours, thepolymer is purified via ultrafiltration (3K MWCO) and dried viafreeze-dry. 7.5 g of final product is obtained. The MW of theprepolymer: 12360 g/mol (¹H NMR); The double bond content: 0.081 meq/g(based on ¹H NMR).

The same chemistry can be used for other carboxylic acid derivativessuch as 4-pentenoic acid.

Example 4

Actinically-crosslinkable prepolymers are prepared according to scheme 4as follows.

A. Synthesis of PDMS/PHEA Multiblock Copolymers

10 g (2.1 mmol) of tetrafunctional PDMS macroinitiator (4816 g/mol), 18mL (157 mmol) of HEA, 0.04 g (0.19 mmol) of CuBr₂, 0.5 mL (1.9 mmol) ofMe₆TREN, and 120 mL of t-amyl alcohol are added to a 250 ml of Schlenkflask. After 4 cycles of freeze-pump-thaw (20 minutes per cycle), 0.24 g(1.7 mmol) of CuBr is added to the flask under the positive N₂ flow. Thereaction is carried out at 40° C. in the oil bath. The monomerconversion is monitored by gas chromatography. At a certain monomerconversion, the reaction is stopped by opening the flask to air. Thereaction mixture is diluted with THF and passed through a neutralalumina oxide column. After addition of 5 mg of 4-methoxyphenol, thesolvent is removed by rotavap. The concentrated solution is thenprecipitated into acetonitrile (800 mL). After filtration, polymer (13g) is obtained. The obtained polymer of PDMS/PHEA multiblock copolymerhas a molecular weight of 10500 g/mol (1H NMR) and 46 w % PDMS andMn=9421 g/mol and PDI=1.45 (GPC).

B. Synthesis of PDMS/PHEA Macromer Containing Multi-Acrylate Groups

6 g (0.57 mmol) of PDMS/PHEA multiblock copolymer is dissolved in 30 mLof THF in a 100 mL round bottom flask, followed by addition of 0.37 mL(5.1 mmol) of acrylic acid. 0.76 mL (5.1 mmol) of DBU in 10 mL of THF isthen slowly added to the reaction solution within 30 minutes. Afterreaction for 45 hours at room temperature, the solution is diluted with600 mL of a mixture of 2-propanol and water (10 v % 2-propanol inwater). The polymer is purified by ultrafiltration (3K MWCO). The finalpolymer powder (5 g) is obtained after freeze-dry. The MW of theprepolymer: 10386 g/mol (1H NMR); The double bond content: 0.270 meq/g(based on ¹H NMR).

C. Synthesis of PDMS/PHEA Macromer Containing Multi-Ene Groups

14 g (1.3 mmol) of PDMS/PHEA multiblock copolymer is dissolved in 50 mLof THF in a 100 mL round bottom flask, followed by addition of 1.6 mL(15.9 mmol) of 4-pentenoic acid. 2.4 mL (15.9 mmol) of DBU in 10 mL ofTHF is then slowly added to the reaction solution within 30 minutes.After reaction for 45 hours at room temperature, the solution is dilutedwith 600 mL of a mixture of 2-propanol and water (10 v % of 2-propanolin water). The polymer is purified by dialysis (1K MWCO) in water. Thefinal polymer powder (9.5 g) is obtained after freeze-dry. The MW of theprepolymer: 10500 g/mol (1H NMR); The double bond content: 0.358 meq/g(based on ¹H NMR).

Example 5 A. Lenses Made from PHEA-PDMS-PHEA Macromer ContainingAcrylate Groups

3 g of the prepolymer synthesized in Example 3B and 7.5 mg of Irgacure2959 are dissolved in 15 mL of 1-propanol. After filtration through amicrofilter with 5 μm pores, the solution is concentrated to 59% ofsolid content via rotavap. The formulation is placed in molds under UVlight for 15 seconds. After removing the lens from the molds, contactlens are hydrated.

B. Lenses Made from PDMS/PHEA Prepolymer Containing Multi-Ene Groups

8.7 g (0.358 meg/g, based on 1HNMR) of the prepolymer synthesized inExample 4C and 21.8 mg of Irgacure 2959 are dissolved in 30 mL of t-amylalcohol. After filtration through a microfilter with 5 μm pores, thesolution is concentrated to 61% of solid content via rotavap. In orderto obtain the stoichiometric ratio between thiol to ene, photo-rheologyis carried out on small size formulation samples by varying the ratio ofthiol to ene. Three 0.2 g of formulation samples are mixed with 3.65 mg,4.01 mg, and 4.4 mg of 3,6-Dioxane-1,8-octane-dithiol, respectively. Theremaining 11.43 g formulation is used for lens cast in the presence of0.17 g (1.87 mmol) of dithiol. The formulation is placed in molds underUV light for 11 seconds. After removing the lens from the molds, contactlens are hydrated.

Components Formulation A Formulation B Prepolymer (Ex. 3B) Example 3BExample 4C MW (g/mol) 12,360 10,152 (double bond content meq/g) (0.113)(0.358) Macromer content (%) 59 61.00 Irgacure 2959 (% vs. macromer)0.25 0.25 DOD 1.66 Solvent (%) 41 37 DOD =3,6-Dioxane-1,8-octane-dithiol

C. Lens Characterization Results

Lens A Lens B Photo-curing (s) 15 11 Water content (%) 57 42 Thickness(μm) 97 110 Modulus (Mpa) 0.82 1.85 Max elongation (%) 33 91 Toughness(kJ/m³) 37 420

What is claimed is:
 1. An actinically crosslinkable prepolymer offormula (1) or (2)

in which r₁ is an integer of 2 or 3, r₂ and r₂′ are either 0 or 1provided that (r₂+r₂′)=1; G₁ and G₂ independent of each other are alinear or branched C₁-C₁₀alkylene divalent radical, a divalent radicalof

 in which q is an integer of from 1 to 5 and alk and alk′ independent ofeach other is a C₁-C₆ alkylene divalent radical, or a divalent radicalof —R′₁—X₅-E-X₆—R′₂— in which R′₁ and R′₂ independent of each other is alinear or branched C₁-C₁₀ alkylene divalent radical or a divalentradical of

 as defined above, X₅ and X₆ independent of each other are a linkageselected from the group consisting of

 in which R′ is H or C₁-C₈ alkyl, E is an alkyl diradical, a cycloalkyldiradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or anaryl diradical with up to 40 carbon atoms which may have ether, thio, oramine linkages in the main chain, provided that if r₂ is 0, then r₁ isinteger 2 or 3 and G₂ is a linear or branched C₁-C₁₀ alkyl radical or amonovalent radical of

 in which q and alk′ are defined as above and alk″ is C₁-C₆ alkyl; X₁and X₂ independent of each other are a linkage selected from the groupconsisting of a direct bond,

 in which R′ is H or C₁-C₈ alkyl; PDMS is a polysiloxane divalentradical of formula (3)

in which ν is 0 or 1, ω is an integer of from 0 to 5, U₁ and U₂independent of each other represent a divalent radical of—R′₁—X₅-E-X₆—R′₂— as defined above or a divalent radical of

 as defined above, D₁, D₂ and D₃ independently of each other are adivalent radical selected from the group consisting of—(CH₂CH₂O)_(t)—CH₂CH₂— in which t is an integer of 3 to 40,—CF₂—(OCF₂)_(a)—(OCF₂CF₂)_(b)—OCF₂— in which a and b independent of eachother is an integer of 0 to 10 provided that a+b is a number in therange of 10 to 30, and a divalent group of formula (4)

in which R₃, R₄, R₅′, R₆, R₇, R₈, R₉ and R₁₀, independently of oneanother, are C₁-C₈-alkyl, C₁-C₄ alkyl- or C₁-C₄-alkoxy-substitutedphenyl, fluoro(C₁-C₁₈-alkyl), cyano(C₁-C₁₂-alkyl),-alk-(OCH₂CH₂)_(n)—OR₁₁ in which alk is C₁-C₆-alkylene divalent radical,R₁₁ is C₁-C₆ alkyl and n is an integer from 1 to 10, m and pindependently of each other are an integer of from 2 to 698 and (m+p) isfrom 5 to 700, provided that at least one of D₁, D₂ and D₃ isrepresented by formula (4); L₁ and L₂ independent of each other are anorganic radical having a valence of (r₁+1), where the organic radical isa linear or branched C₁-C₁₄ aliphatic radical, a C₅-C₄₅ cycloaliphaticor aliphatic-cycloaliphatic di-, tri-, or tetra-valent radical, or aC₆-C₂₄ aromatic or araliphatic di-, tri-, or tetra-valent radical,provided that each of L₁ and L₂ has valence of (r₁+1); and A₁ and A₂independently of each other are a monovalent radical of formula (5)

in which r₄ is an integer of 0 or 1; X₇ is —O— or

 in which R′ is H or C₁-C₈ alkyl; X₈ is a linkage selected from thegroup consisting of

 in which R′ is H or C₁-C₈ alkyl; G₅ is a linear or branched C₁-C₁₀alkylene divalent radical, a divalent radical of

 as defined above, or a divalent radical of —R′₁—X₅-E-X₆—R′₂— as definedabove; G₆ is a C₂-C₆ alkylene divalent radical; LC is a divalent radicalof a linear polymer chain of one or more hydrophilic vinylic monomers;and AX is a thiol group or a radical of formula —X₈-G₇-X₉-Q, in which:X₈ is an linkage as defined above; G₇ is a direct bond or a linear orbranched alkylene divalent radical; X₉ is a direct bond or a linkageselected from the group consisting of

 Q is an acryloyl group, a methacryloyl group, a vinyl group, an allylgroup, or a norbornenyl group.
 2. The prepolymer of claim 1, wherein LCis a divalent radical of a linear polymer chain of one or morehydrophilic vinylic monomers selected from the group consisting ofN,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolicacid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide,N-[tris(hydroxymethyl)methyl]-acrylamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,1-n-propyl-3-methylene-2-pyrrolidone,1-n-propyl-5-methylene-2-pyrrolidone,1-isopropyl-3-methylene-2-pyrrolidone,1-isopropyl-5-methylene-2-pyrrolidone,1-n-butyl-3-methylene-2-pyrrolidone,1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl methacrylate,2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, trimethylammonium 2-hydroxy propylmethacrylatehydrochloride, aminopropyl methacrylate hydrochloride,dimethylaminoethyl methacrylate, glycerol methacrylate,N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, aC₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight averagemolecular weight of up to 1500, methacrylic acid, N-vinyl formamide,N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide,allyl alcohol, N-vinyl caprolactam, and mixtures thereof.
 3. Theprepolymer of claim 2, wherein LC is a divalent radical of a linearpolymer chain composed of monomeric units of N,N-dimethylacrylamide orN,N-dimethylacrylamide and one or more hydrophilic vinylic monomer otherthan N,N-dimethylacrylamide.
 4. The prepolymer of claim 2, wherein LC isa divalent radical of a linear polymer chain composed of monomeric unitsof N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or more hydrophilicvinylic monomer other than N-Vinylpyrrolidone.
 5. The prepolymer ofclaim 2, wherein LC is a divalent radical of a linear polymer chaincomposed of monomeric units of 3-acryloylamino-1-propanol,N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide,2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA),hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerolmethacrylate (GMA), allyl alcohol, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500,or a combination thereof.
 6. The prepolymer of claim 2, wherein theprepolymer is represented by formula (1) in which r₂ is zero, and G₂ isa linear or branched C₁-C₁₀alkyl radical or a monovalent radical of

in which q and alk′ are defined as above and alk″ is C₁-C₆ alkyl.
 7. Theprepolymer of claim 2, wherein the prepolymer is represented by formula(1) in which r₂ is an integer of
 1. 8. An actinically crosslinkableprepolymer of formula (2)

in which r₁ is an integer of 1 to 3, r₃ is an integer of 3 or 4; G₃ andG₄ independent of each other are a linear or branched C₁-C₁₀ alkylenedivalent radical, a divalent radical of

 in which q is an integer of from 1 to 5 and alk and alk′ independent ofeach other is a C₁-C₆ alkylene divalent radical, or a divalent radicalof —R′₁—X₅-E-X₆—R′₂— in which R′₁ and R′₂ independent of each other is alinear or branched C₁-C₁₀ alkylene divalent radical or a divalentradical of

 as defined above, X₅ and X₆ independent of each other are a linkageselected from the group consisting of

 in which R′ is H or C₁-C₈ alkyl, E is an alkyl diradical, a cycloalkyldiradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or anaryl diradical with up to 40 carbon atoms which may have ether, thio, oramine linkages in the main chain, X₃ and X₄ independent of each otherare a linkage selected from the group consisting of a direct bond,

 in which R′ is H or C₁-C₈ alkyl; PDMS is a polysiloxane divalentradical of formula (3)

in which ν is 0 or 1, ω is an integer of from 0 to 5, U₁ and U₂independent of each other represent a divalent radical of—R′₁—X₅-E-X₆—R′₂— as defined above or a divalent radical of

 as defined above, D₁, D₂ and D₃ independently of each other are adivalent radical selected from the group consisting of—(CH₂CH₂O)_(t)—CH₂CH₂— in which t is an integer of 3 to 40,—CF₂—(OCF₂)_(a)—(OCF₂CF₂)_(b)—OCF₂— in which a and b independent of eachother is an integer of 0 to 10 provided that a+b is a number in therange of 10 to 30, and a divalent group of formula (4)

in which R₃, R₄, R₅′, R₆, R₇, R₈, R₉ and R₁₀, independently of oneanother, are C₁-C₈-alkyl, C₁-C₄ alkyl- or C₁-C₄-alkoxy-substitutedphenyl, fluoro(C₁-C₁₈-alkyl), cyano(C₁-C₁₂-alkyl),-alk-(OCH₂CH₂)_(n)—OR₁₁ in which alk is C₁-C₆-alkylene divalent radical,R₁₁ is C₁-C₆ alkyl and n is an integer from 1 to 10, m and pindependently of each other are an integer of from 2 to 698 and (m+p) isfrom 5 to 700, provided that at least one of D₁, D₂ and D₃ isrepresented by formula (4); L₃ is an organic radical having a valence of(r₁+1), where the organic radical is a linear or branched C₁-C₁₄aliphatic radical, a C₅-C₄₅ cycloaliphatic or aliphatic-cycloaliphaticdi-, tri-, or tetra-valent radical, or a C₆-C₂₄ aromatic or araliphaticdi-, tri-, or tetra-valent radical, provided that L₃ has valence of(r₁+1); B₁ is a multivalent organic radical having a valence of r₃; andA₃ is a monovalent radical of formula (5)

in which r₄ is an integer of 0 or 1; X₇ is —O— or

 in which R′ is H or C₁-C₈ alkyl; X₈ is a linkage selected from thegroup consisting of

 in which R′ is H or C₁-C₈ alkyl; G₅ is a linear or branched C₁-C₁₀alkylene divalent radical, a divalent radical of

 as defined above, or a divalent radical of —R′₁—X₅-E-X₆—R′₂— as definedabove; G₆ is a C₂-C₆ alkylene divalent radical; LC is a divalent radicalof a linear polymer chain of one or more hydrophilic vinylic monomers;and AX is a thiol group or a radical of formula —X₈-G₇-X₉-Q, in which:X₈ is an linkage as defined above; G₇ is a direct bond or a linear orbranched alkylene divalent radical; X₉ is a direct bond or a linkageselected from the group consisting of

 Q is an acryloyl group, a methacryloyl group, a vinyl group, an allylgroup, or a norbornenyl group.
 9. The prepolymer of claim 8, wherein LCis a divalent radical of a linear polymer chain of one or morehydrophilic vinylic monomers selected from the group consisting ofN,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolicacid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide,N-[tris(hydroxymethyl)methyl]-acrylamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,1-n-propyl-3-methylene-2-pyrrolidone,1-n-propyl-5-methylene-2-pyrrolidone,1-isopropyl-3-methylene-2-pyrrolidone,1-isopropyl-5-methylene-2-pyrrolidone,1-n-butyl-3-methylene-2-pyrrolidone,1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate,2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, trimethylammonium 2-hydroxy propylmethacrylatehydrochloride, aminopropyl methacrylate hydrochloride,dimethylaminoethyl methacrylate, glycerol methacrylate,N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, aC₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight averagemolecular weight of up to 1500, methacrylic acid, N-vinyl formamide,N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide,allyl alcohol, N-vinyl caprolactam, and mixtures thereof.
 10. Theprepolymer of claim 9, wherein LC is a divalent radical of a linearpolymer chain composed of monomeric units of N,N-dimethylacrylamide orN,N-dimethylacrylamide and one or more hydrophilic vinylic monomer otherthan N,N-dimethylacrylamide.
 11. The prepolymer of claim 9, wherein LCis a divalent radical of a linear polymer chain composed of monomericunits of N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or morehydrophilic vinylic monomer other than N-Vinylpyrrolidone.
 12. Theprepolymer of claim 9, wherein LC is a divalent radical of a linearpolymer chain composed of monomeric units of 3-acryloylamino-1-propanol,N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide,2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA),hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerolmethacrylate (GMA), allyl alcohol, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500,or a combination thereof.
 13. The prepolymer of claim 9, wherein informula (2) r₃ is an integer of 3.